(19)
(11) EP 1 203 653 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
27.06.2007 Bulletin 2007/26

(21) Application number: 01932106.6

(22) Date of filing: 17.05.2001
(51) International Patent Classification (IPC): 
B01J 35/00(2006.01)
B01J 35/02(2006.01)
G02B 1/10(2006.01)
G02F 1/15(2006.01)
C03C 17/36(2006.01)
A47G 1/00(2006.01)
G02B 5/08(2006.01)
(86) International application number:
PCT/JP2001/004104
(87) International publication number:
WO 2001/087593 (22.11.2001 Gazette 2001/47)

(54)

COMPOSITE MATERIAL

VERBUNDWERKSTOFF

MATERIAU COMPOSITE


(84) Designated Contracting States:
DE FR GB IT

(30) Priority: 17.05.2000 JP 2000145395

(43) Date of publication of application:
08.05.2002 Bulletin 2002/19

(73) Proprietor: Murakami Corporation
Shizuoka-shi, Shizuoka, 422-8065 (JP)

(72) Inventors:
  • Kikuchi, Hideyuki
    Shizuoka-shi, Shizuoka 420-0911 (JP)
  • Komatsu, Toru
    Shimada-shi, Shizuoka 427-0017 (JP)
  • Kobayashi, Masaki
    Fujieda-shi, Shizuoka 426-0037 (JP)

(74) Representative: Goddar, Heinz J. 
FORRESTER & BOEHMERT Pettenkoferstrasse 20-22
80336 München
80336 München (DE)


(56) References cited: : 
EP-A- 0 950 568
EP-A- 1 003 067
EP-A1- 0 820 967
JP-A- 10 329 261
JP-A- 2000 131 513
EP-A- 0 978 494
EP-A- 1 099 671
JP-A- 10 297 436
JP-A- 11 092 146
   
       
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a composite material the surface of which is made to be hydrophilic or antifouling by forming a film layer containing a photocatalytic substance on a material surface of a substrate, a lens, a glass plate, a mirror, etc, improving the hydrophilicity or antifouling property of the material surface.

    Background Art



    [0002] A technique, which keeps a surface of a material clean by forming a photocatalytic substance layer on a material surface, has been known. This technique enables removing dirt easily by decomposing dirt adhering to the material surface using a photocatalytic action of a photocatalytic substance layer provided on the material surface and by rinsing the material surface with water or the like.

    [0003] As a composite material employing a material surface cleaning technique using such a photocatalytic substance layer, there was one which was proposed by Japanese Patent Laid-open No.H10-36144 applied for by this applicant. Its structure is described, referring to cross-sectional drawing Figure 2. In this, a surface is made hydrophilic by providing a SiO2 film 6 porously on the surface of a base material 2. A surface of a SiO2 film 6 is originally hydrophilic, the hydrophilicity, however, is improved by making the surface porous. With a SiO2 film 6 exclusively provided, hydrophilicity decreases with dirt adhering to the surface if it is exposed to the air for a long period of time. Accordingly, by providing a TiO2 film 4 between a SiO2 film 6 and a base material 2, the photocatalytic decomposition action of the TiO2 4 film is used to decompose dirt adhering to the surface of a SiO2 film 6 and to keep the surface of a SiO2 film 6 clean, maintaining the hydrophilicity.

    [0004] Figure 3 shows a graph indicating spectral reflectance characteristics in a visible region (380~780nm) in a conventional structure shown in Figure 2 with a SiO2 film thickness made at 10nm and when a film thickness of a TiO2 film 4 changes to 50, 100, 150, and 200nm. Figure 4 shows a graph indicating spectral reflectance characteristics with like samples. As shown in Figure 3 and Figure 4, when a film thickness of a TiO2 film 4 is 50nm, relatively flat reflectance characteristics and transmittance characteristics were obtained, while the amplitude in reflectance increases with a film thickness of 100, 150, and 200nm as wavelengths change.

    [0005] Additionally, Table 1 shows initial contact angles and contact angles after being exposed to black light with an intensity of 1mW/cm2 for four hours when oil is applied onto each material surface of a TiO2 film 4, using samples prepared in a conventional structure shown in Figure 2 with a film thickness of 50, 100 or 150nm similar to Figure 3 and Figure 4 respectively.
    <Table 1>
    TiO2 Film Thickness (in nm) Initial Contact Angle (in degree) Contact Angle after being exposed to black light (in degree)
    50 87.7 72.1
    100 86.6 8.3
    150 85.6 7.9


    [0006] EP-A-0 978 494 discloses a glass substrate with a thin metal film having a thickness of several tenths nm formed by secondary sputtering and a photocatalyzing TiO2 film and a porous SiO2 film formed on the thin metal film.

    Disclosure of Invention



    [0007] As can be seen from the results of Table 1, for a hydrophilic material using the above-stated photocatalytic substance, a photocatalytic substance film 4 with a film thickness of 100nm or more is required to obtain a photocatalytic decomposition action to maintain hydrophilicity. As shown in Figure 3, however, when a film thickness of a TiO2 film 4 is 100, 150 or 200nm, a coloring action takes place on a material surface due to increased amplitude occurring in spectral characteristics. This is because optical interference in a visible light region occurs at a TiO2 film 4 due to formation of a thick TiO2 film 4. Thus, if the amplitude in spectral characteristics is large, the color tone of an original material surface is spoiled. Additionally, to provide a thick film thickness, more photocatalytic substance material is required.

    [0008] The present invention has been realized in consideration of the above-mentioned points, to provide a composite material which can obtain sufficient antifouling properties or hydrophilicity even when a photocatalytic substance film is thinner than a conventional film. Thus an optical interference action in a photocatalytic substance is suppressed and an amount of a photocatalytic substance to be used is decreased.

    [0009] The present invention possesses a base material, a transparent metal thin film provided on the surface of the base material, having a thickness of between 1,0 and 10,0 nm and a hydrophilic functional layer containing a photocatalytic substance provided on a surface of the transparent metal thin film wherein the transparent metal thin film reflects ultraviolet rays to re-enter the photocatalyst containing layer. According to experiments conducted by inventors, it was found that, by providing a transparent metal thin film, a photocatalytic property improves. Due to this, because hydrophilicity or antifouling can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is thinner than conventional layers, an amount of a photocatalytic substance to be used can be reduced. Additionally, by making a hydrophilic functional layer containing a photocatalytic substance thinner, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced and the color tone of a base material can be maintained.

    Brief Description of Drawings



    [0010] 

    Figure 1 is a cross-sectional view showing Embodiment 1 for carrying out the present invention.

    Figures 2 is a cross-sectional view showing a conventional defogging mirror.

    Figures 3 is a graph indicating reflectance characteristics of a TiO2 film at thicknesses of 50, 100, 150 and 200nm in a conventional defogging mirror.

    Figures 4 is a graph indicating transmittance characteristics of a TiO2 film thicknesses of 50, 100, 150 and 200nm in a conventional defogging mirror.

    Figure 5 is a graph indicating transmittance characteristics when Cr is used for a transparent metal thin film of the embodiment shown in Figure 1.

    Figure 6 is a graph indicating transmittance characteristics when Rh is used for a transparent metal thin film of the embodiment shown in Figure 1.

    Figure 7 is a graph indicating transmittance characteristics when Ag is used for a transparent metal thin film of the embodiment shown in Figure 1.

    Figure 8 is a graph of transmittance characteristics when Pt is used for a transparent metal thin film of the embodiment shown in Figure 1.

    Figure 9 is a graph of transmittance characteristics when A1 is used for a transparent metal thin film of the embodiment shown in Figure 1.

    Figure 10 is a cross-sectional view showing Embodiment 2 of the present invention.

    Figure 11 is a cross-sectional view showing Embodiment 3 of the present invention.

    Figure 12 is a cross-sectional view showing Embodiment 4 of the present invention.

    Figure 13 is a cross-sectional view showing a conventional colored mirror.

    Figure 14 is a cross-sectional view showing a colored defogging mirror which combines a hydrophilic layer shown in Figure 2 with the colored mirror shown in Figure 13.

    Figure 15 is a graph of reflectance characteristics of Embodiment 4 of the present invention shown in Figure 12, the colored mirror shown in Figure 13 and the colored defogging mirror shown in Figure 14.

    Figure 16 is a cross-sectional view showing Embodiment 5 of the present invention.

    Figure 17 is a cross-sectional view showing Embodiment 6 of the present invention.

    Figure 18 is a cross-sectional view showing Embodiment 7 of the present invention.

    Figure 19 is a cross-sectional view showing a conventional solid-phase electrochromic glare-proof mirror.

    Figure 20 is a cross-sectional view showing a solid-phase electrochromic glare-proof defogging mirror which combines a hydrophilic film shown in Figure 2 with the solid-phase electrochromic glare-proof mirror shown in Figure 19.

    Figure 21 is a graph of reflectance characteristics of Embodiment 7 of the present invention shown in Figure 18, the solid-phase electrochromic glare-proof mirror shown in Figure 19 and the solid-phase electrochromic glare-proof defogging mirror shown in Figure 20.

    Figure 22 is a cross-sectional view showing Embodiment 8 of the present invention.

    Figure 23 is a cross-sectional view showing Embodiment 9 of the present invention.

    Figure 24 is a cross-sectional view showing Embodiment 10 of the present invention.



    [0011] In the figures, the symbols indicate the following:

    22: Light-transmitting plate material, 24: Transparent metal thin film, 26: Hydrophilic functional layer containing a photocatalytic substance, 28: Photocatalytic layer containing a photo catalytic substance, 30: Hydrophilic layer containing a hydrophilic substance, 34: Mixed layer containing a photocatalytic substance and a hydrophilic substance, 40: Reflection film, 42: Transparent electrode film, 44: Solid-phase electrochromic layer, 46: Electrode-reflection dual function film, 52: Liquid-phase electrochromic layer, 54: First transparent electrode film, 56: Second transparent electrode film.


    Best Mode for Carrying Out the Invention



    [0012] The present invention is summarized above. Additionally, in the present invention, the above-mentioned base material can comprise a light-transmitting material.

    [0013] Additionally, in the present invention, the above-mentioned base material can comprise a plate material.

    [0014] Additionally, in the present invention, the above-mentioned base material can comprise a light-transmitting plate material. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced and the original optical transparency of the light-transmitting plate material can be maintained.

    [0015] Additionally, the present invention can be constructed as a defogging mirror by providing a reflection film on the back of the above-mentioned light-transmitting plate material (which is a surface on which the above-mentioned transparent metal thin film is not provided). Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced and the color tone of a reflected image by a reflection film can be maintained.

    [0016] The above-mentioned light-transmitting plate material comprises a light-transmitting colored plate material having light wavelength selectivity. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced and an transparent plate defogging material which maintains the original color tone of the light-transmitting colored plate material can be provided.

    [0017] By providing a reflection film on the back of the above-mentioned light-transmitting plate material, a defogging mirror can be constructed. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced and a defogging mirror which maintains the original color tone of the light-transmitting colored plate material can be provided.

    [0018] Additionally, in the present invention, the above-mentioned light-transmitting plate material can be constructed by providing a liquid-phase electrochromic layer between two light-transmitting substrates and transparent electrode films on a respective surface opposite to the above-mentioned two light-transmitting substrates. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced, and a defogging material, which does not interfere with a color antiglare action of the liquid-phase electrochromic layer, can be provided.

    [0019] By providing a reflection film on the back of the above-mentioned light-transmitting plate material, a defogging mirror can be constructed. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced, and a defogging mirror, which does not interfere with a color antiglare action of the liquid phase electrochromic layer, can be provided.

    [0020] Additionally, in the present invention, the above-mentioned light-transmitting plate material can be constructed by forming in laminated layers the first transparent electrode film, a solid-phase electrochromic layer and the second transparent electrode film in consecutive order on the back of the light-transmitting substrate. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced, and a defogging material, which does not interfere with a color antiglare action of the solid-phase electrochromic layer, can be provided.

    [0021] Additionally, in the present invention, the above-mentioned plate material can be constructed by forming in laminated layers a transparent electrode film, a solid-phase electrochromic layer and an electrode-reflection dual function film in consecutive order on the back of the light-transmitting substrate. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced, and a defogging mirror, which does not interfere with a color antiglare action of the solid-phase electrochromic layer, can be provided. Additionally, because the above-mentioned electrode-reflection dual function film serve both as an electrode film and a reflection film, it is not necessary to provide both films and manufacturing and material costs can be reduced.

    [0022] Alternatively, in the present invention, a plate material is formed as a defogging mirror, in which a light-transmitting substrate with a transparent electrode film provided on one side and a substrate with an electrode-reflection dual function film provided on the other side are placed so that the transparent electrode film and the electrode-reflection dual function film face each other, and a liquid-phase electrochromic layer is provided between the light-transmitting substrate and the substrate. Accordingly, because sufficient photocatalytic performance can be obtained even if a hydrophilic functional layer containing a photocatalytic substance is made thin, optical interference in a hydrophilic functional layer containing the photocatalytic substance can be reduced, and a defogging mirror, which does not interfere with a color antiglare action of the solid-phase electrochromic layer, can be provided. Additionally, because the above-mentioned electrode-reflection dual function film serve both as an electrode film and a reflection film, it is not necessary to provide both films and manufacturing and material costs can be reduced.

    [0023] Additionally, a defogging mirror using a composite material according to the present invention can be structured as an outer mirror for automobile use.

    [0024] A hydrophilic functional layer containing the above-mentioned photocatalytic substance can comprise, from the side of the above-mentioned base material, a laminate of a photocatalytic layer containing a photocatalytic substance and a hydrophilic layer containing a hydrophilic substance as its main element.

    [0025] A layer thickness of a hydrophilic layer the above-mentioned hydrophilic substance can be 50nm or less.

    [0026] A hydrophilic functional layer containing the above-mentioned photocatalytic substance can comprise a mixed layer containing a photocatalytic substance and a hydrophilic substance as its main element.

    [0027] The main component of the above-mentioned photocatalytic substance can be TiO2 and the main component of the above-mentioned hydrophilic substance can be SiO2.

    [0028] A hydrophilic functional layer containing the above-mentioned photocatalytic substance can comprise a layer the main component of which is a photocatalytic substance.

    [0029] The main component of the above-mentioned photocatalytic substance can be TiO2.

    [0030] The surface of a hydrophilic functional layer containing the above-mentioned photocatalytic substance can be constructed porously. Accordingly, because the surface is porous, hydrophilicity can be further improved.

    [0031] The above-mentioned transparent metal thin film can comprise, for example, Cr, Rh, Ag, Pt, Al or a mixture of these as its main component.

    [0032] In the present invention, a transparent metal thin film is a metal thin film which is transparent in a visible light region, and it can be formed, for example, by making a metallic substance thin, scattering minute metallic particles in an island shape or disposing them in a lattice shape by patterning or the like Furthermore, this transparent metal thin film is not necessarily colorless. Additionally, a film thickness, transmittance and color of this transparent metal thin film can be made diversely within the bounds where transparency can be obtained and effects to improve photocatalytic performance of a photocatalytic substance can be obtained. Additionally, although this transparent metal thin film may exhibit reflection depending on a film thickness or the like, a composite material according to the present invention does not include those materials which are constructed for use as a mirror using this transparent metal thin film as a reflection film.

    [0033] Various embodiments for carrying out the present invention are described in the following:

    Embodiment 1



    [0034] Figure 1 shows a cross-sectional drawing of Embodiment 1 for carrying out a defogging material according to the present invention. On the surface of a light-transmitting plate material 22 comprising a resin, glass, or the like, a transparent metal thin film 24 comprising Cr, Rh, or the like is formed using a vacuum deposition method, sputtering method, or the like Furthermore, on the surface of a transparent metal thin film 24, a hydrophilic functional layer 26 containing a photocatalytic substance is provided. A hydrophilic functional layer 26 containing a photocatalytic substance is constructed by forming in laminated layers, from the side of the transparent metal thin film 24, a photocatalytic layer 28 containing a photocatalytic substance comprising TiO2 or the like and a hydrophilic layer 30 containing a hydrophilic substance comprising SiO2 or the like using a vacuum deposition method, sputtering method, or the like Alternatively, in the embodiment of this embodiment, to improve hydrophilicity further, the surface of a hydrophilic layer 30 containing a hydrophilic substance can be formed porously.

    [0035] Table 2 shows initial contact angles and contact angles after being exposed to black light with an intensity of 1mW/cm2 for four hours when oil is applied to each material surface, using samples prepared in a structure shown in Figure 1 with a film thickness of 0 (no film formed), 1.0, 2.0 or 5.0nm, respectively, using Cr for a transparent metal thin film 24. At this time, a photocatalytic layer 28 containing a photocatalytic substance is formed using TiO2 at a film thickness of 50nm, a hydrophilic layer 30 containing a hydrophilic substance is formed of SiO2 at a film thickness of 10nm.
    <Table 2>
    Cr Film Thickness (in nm) Initial Contact Angle (in degrees) Contact Angle after being exposed to black light (in degrees)
    0 (None) 87.7 72.1
    1.0 87.0 49.3
    2.0 85.5 7.7
    5.0 88.5 5.0


    [0036] When the thickness of a Cr film was 0nm (no Cr film was formed), the decrease in a contact angle from the initial state was approximately 15 degrees after being exposed to black light for four hours. However, when the thickness of a Cr film is 5.0nm, the decrease was more than 80 degrees. It can be seen that by providing a transparent metal thin film 24, a photocatalytic property has improved, the decomposition action of oil applied to the surface has been facilitated, and the hydrophilicity of a base material surface has substantially been restored.

    [0037] Table 3 shows similar contact angle measurement results by preparing samples using Rh as a transparent metal thin film 24 in the structure shown in Figure 1 with a film thickness of 0 (no film was formed), 0.5, 1.0 and 5.0nm, respectively. When the film thickness of an Rh film was 0nm (no Rh film was formed), the decrease in a contact angle from the initial state was approximately 15 degrees after being exposed to black light for four hours. However, when the thickness of an Rh film was 5.0nm, the decrease was more than 50 degrees, and it can be seen that the hydrophilicity of a base material surface substantially been restored.
    <Table 3>
    Rh Film Thickness (in nm) Initial Contact Angle (in degrees) Contact Angle after being exposed to black light (in degrees)
    0 (None) 87.7 72.1
    0.5 90.0 58.1
    1.0 85.2 43.3
    5.0 88.0 30.4


    [0038] Table 4 shows similar contact angle measurement results by preparing samples using Ag as a transparent metal thin film 24 in the structure shown in Figure 1 with a film thickness of 0 (no film was formed), 1.0, 2.0 and 5.0nm, respectively. When the film thickness of an Ag film was 0nm (no Ag film was formed), the decrease in a contact angle from the initial state was approximately 15 degrees after being exposed to black light for four hours. However, when the thickness of an Ag film was 5.0nm, the decrease was more than 50 degrees, and it can be seen that the hydrophilicity of a base material surface substantially been restored.
    <Table 4>
    Ag Film Thickness (in nm) Initial Contact Angle (in degrees) Contact Angle after being exposed to black light (in degrees)
    0 (None) 87.7 72.1
    1.0 88.4 53.0
    2.0 86.6 42.0
    5.0 87.5 34.5


    [0039] Table 5 shows similar contact angle measurement results by preparing samples using Pt as a transparent metal thin film 24 in the structure shown in Figure 1 with a film thickness of 0 (no film was formed), 1.0, 2.0 and 5.0nm, respectively. When the film thickness of a Pt film was 0nm (no Pt film was formed), the decrease in a contact angle from the initial state was approximately 15 degrees after being exposed to black light for four hours. However, when the thickness of a Pt film was 5.0nm, the decrease was more than 50 degrees, and it can be seen that the hydrophilicity of a base material surface substantially been restored.
    <Table 5>
    Pt Film Thickness (in nm) Initial Contact Angle (in degrees) Contact Angle after being exposed to black light (in degrees)
    0 (None) 87.7 72.1
    1.0 85.6 56.2
    2.0 87.5 45.1
    5.0 88.3 31.5


    [0040] Table 6 shows similar contact angle measurement results by preparing samples using Al as a transparent metal thin film 24 in the structure shown in Figure 1 with a film thickness of 0 (no film was formed), 2.0, 5.0, and 10.0nm, respectively. When the film thickness of an A1 film was 0nm (no Al film was formed), the decrease in a contact angle from the initial state was approximately 15 degrees after being exposed to black light for four hours. However, when the thickness of an A1 film was 10.0nm, the decrease was more than 50 degrees, and it can be seen that the hydrophilicity of a base material surface substantially been restored.
    <Table 6>
    Al Film Thickness (in nm) Initial Contact Angle (in degrees) Contact Angle after being exposed to black light (in degrees)
    0 (None) 87.7 72.1
    2.0 86.2 58.4
    5.0 88.0 44.1
    10.0 87.4 36.9


    [0041] The details of an effect of improving a photocatalytic property by a transparent metal thin film have not been made clear. From the available data, it is thought that: When a photocatalytic substance is excited by ultraviolet rays absorbed in a photocatalyst layer, electrons and corresponding holes are generated within a photocatalytic substance layer. Although some of these electrons and corresponding holes disappear by pairing up (recombination), remaining electrons and corresponding holes move to a material surface, generate O2- (superoxide anion) with a strong oxidizing force and OH (hydroxy radical) by reacting with air and moisture on the material surface, and cause oxidative degradation of organic matter adhering to the material surface. The transparent thin film when formed exhibits an effect of improving efficiency (electric charge separation efficiency) involved in an oxidation-reduction reaction by reducing disappearing electrons and holes which are paired (recombined). Additionally, because ultraviolet rays reflected by a transparent metal thin film re-enter a photocatalyst layer, thereby increasing photoexcitation occurrences, it is thought that the film has an effect of improving photocatalytic performance.

    [0042] Additionally, light transmittance characteristics in a visible light region (380~780nm) of embodiments shown in Table 2 to Table 6 are shown in Figure 5 to Figure 9. Most of the examples show nearly flat spectral characteristics, and in all of the examples, transmittance of more than 30% is shown with a film thickness of 5.0nm, indicating that in most cases films used are colorless transparent light-transmitting films.

    Embodiment 2



    [0043] Figure 10 shows a cross-sectional drawing of Embodiment 2 of a composite material according to the present invention. On the surface of a light-transmitting plate material 22, a transparent metal thin film 24 comprising Cr, Rh, or the'like is formed using a vacuum deposition method, for example. Furthermore on the transparent metal thin film 24, a hydrophilic layer 32 comprising a photocatalytic substance such as TiO2 or the like is formed using a vacuum deposition method, sputtering method, or the like.

    [0044] Because photocatalytic substances such as TiO2 or the like become hydrophilic by being photoexcited, in Embodiment 2 for carrying out the invention, by forming a hydrophilic layer 32 comprising a photocatalytic substance using a photocatalytic substance such as TiO2 which has hydrophilicity, a material surface can be changed to be hydrophilic and hydrophilicity can be maintained by a photocatalytic decomposition action. Alternatively, in this embodiment for carrying out the invention, to improve hydrophilicity further, the surface of a hydrophilic layer 32 comprising a photocatalytic substance can be formed porously.

    Embodiment 3



    [0045] Figure 11 shows a cross-sectional drawing of Embodiment 3 of a composite material according to the present invention. On the surface of a light-transmitting plate material 22, a transparent metal thin film 24 comprising Cr, Rh, or the like is formed, and on the surface of the transparent metal thin film 24, a mixed layer 34 containing a photocatalytic substance comprising TiO2 or the like and a hydrophilic substance comprising SiO2 or the like is formed using a vacuum deposition method, for example. Alternatively, the surface of the mixed layer 34 containing a photocatalytic substance and a hydrophilic substance can be formed porously.

    [0046] As in the structure shown in Figure 11, by forming a mixed layer 34 containing a photocatalytic substance and a hydrophilic substance, a material surface can be made to become hydrophilic, and hydrophilicity can be maintained by a photocatalytic decomposition action.

    [0047] Alternatively, by forming a reflection film comprising Cr, Al, or the like on the back of a light-transmitting plate material 22 of Embodiments 1 to 3 for carrying out the invention using a vacuum deposition method, sputtering method, or the like, the resulting structure can be used a defogging mirror.

    Embodiment 4



    [0048] Figure 12 shows a cross-sectional drawing of Embodiment 4 of a defogging material according to the present invention. On a light-transmitting plate material 22, the same film structure as shown in Figure 1 is formed. In other words, a transparent metal thin film 24 is formed and furthermore on its surface, a hydrophilic functional layer 26 containing a photocatalytic substance is provided. The hydrophilic functional layer 26 containing a photocatalytic substance comprises, from the side of the transparent metal thin film 24, a photocatalytic layer 28 containing a photocatalytic substance comprising TiO2 or the like and a hydrophilic layer 30 containing a hydrophilic substance comprising SiO2 or the like The above layers are formed in laminated layers by a vacuum deposition method, sputtering method, or the like. Alternatively, in this embodiment for carrying out the invention, to improve hydrophilicity further, the surface of the hydrophilic layer 30 containing a hydrophilic substance can be formed porously. On the back of the light-transmitting plate material 22, optical thin films, a TiO2 film 36, a SiO2 film 38 and a reflection film 40 are formed in laminated layers to be used for a defogging mirror having a selective reflectance characteristics of specific wave lengths and a colored reflection plane. Alternatively, to prevent corrosion of the reflection film 40, a protective coating (not shown) can be provided on the back of the reflection film 40.

    [0049] Next, spectral reflectance characteristics of a mirror shown in Figure 12 and conventional mirrors or the like are described. Here, a mirror shown in Figure 12 is considered to be formed comprising a TiO2 film 36 with a film thickness of 100nm, a SiO2 film 38 with a film thickness of 20nm, a photocatalytic layer 28 containing a photocatalytic substance with a film thickness of 50nm, and a hydrophilic layer 30 containing a hydrophilic substance with a film thickness of 10nm. Figure 13 shows a structure of a section of a conventional colored mirror. This structure is on the surface of a light-transmitting plate material 22 with a structure shown in Figure 12 and does not possess a transparent metal thin film 24 or a hydrophilic functional layer 26 containing a photocatalytic substance. On the back of the light-transmitting plate material 22, a TiO2 film 36, a SiO2 film 38 and a reflection film 40 in the same structure and film thicknesses as these shown in Figure 12 are formed in laminated layers. Here, the film thickness of the TiO2 film 36 is made at 100nm and the film thickness of the SiO2 film 38 is made at 20nm.

    [0050] Figure 14 shows a structure of a section of a colored defogging mirror which combines the conventional hydrophilic film shown in Figure 2 with the conventional colored mirror shown in Figure 13. In this structure, on the surface of a light-transmitting plate material 22 with a conventional colored mirror structure shown in Figure 13, a TiO2 film 4 and a SiO2 film 6 of a conventional defogging mirror shown in Figure 2 are combined. Here, a film thickness of the TiO2 film 4 is made at 200nm and the film thickness of the SiO2 film 6 is made at 10nm.

    [0051] Figure 15 shows spectral reflectance characteristics in a visible region (380~780nm) in structures respectively shown in Figures 12, 13, and 14. Colored mirrors shown in Figures 12 and 13 have the peak reflectance within the limits of 420~480nm in wavelength, and the surface color is blue. Colored mirrors with a blue color are used for mirrors for automobiles, and possess a property of reducing the glare caused by daytime sunlight. Human visibility peaks at a wavelength of 555nm when the surroundings are light, and a yellowish green color can be seen clearly. As the surroundings become dark, the peak of human visibility moves toward the blue color group and reaches a peak wavelength of 505nm. Consequently, since the peak of colored mirrors in the structures shown Figures 12 and 13 is shifted from the peak of human visibility during the daytime, they look slightly dark and prevent glare caused by sunlight. At night, since their peak is consistent with the peak of human visibility, reflected images can be seen brightly and they provide excellent visibility.

    [0052] Since spectral reflectance characteristics of the structure according to the present invention shown in Figure 12 and of the conventional colored mirror structure shown in Figure 13 possess a reflectance peak within the limits of 420~480nm in wavelength, the mirror surface of the structures shown in Figures 12 and 13 is blue. As for spectral reflectance characteristics of a conventional hydrophilic film structure shown in Figure 14, reflectance within the limits of 430~460nm in wavelength decreased. This is because in order to improve a photocatalytic property, the TiO2 film 4 was four times as thick as that of the structure shown in Figure 12, resulting in optical interference in the TiO2 film and dissipating the peak. Thus, in the conventional structure shown in Figure 14, since the surface color of the mirror is not blue, a glare-proof effect is not obtained. In the structure according to the present invention shown in Figure 12, since the film thickness of a photocatalytic layer containing a photocatalytic substance, which corresponds to a conventional TiO2 film, is made thin enough not to be influenced by optical interference, a color of a specific wavelength cannot be obstructed even if a colored mirror having selective reflection characteristics for specific wavelengths is used.

    Embodiment 5



    [0053] Figure 16 shows a cross-sectional drawing of Embodiment 5 of a defogging material according to the present invention. On a light-transmitting plate material 22, the same film structure as shown in Figure 10 is formed. In other words, a transparent metal thin film 24 and a hydrophilic layer 32 comprising a photocatalytic substance are formed. On the back of the light-transmitting plate material 22, similarly to the structure shown in Embodiment 4 (Figure 12), a TiO2 film 36, a SiO2 film 38 and a reflection film 40 are formed in laminated layers. Alternatively, in this embodiment, the surface of the hydrophilic layer 32 containing a photocatalytic substance can be formed porously.

    Embodiment 6



    [0054] Figure 17 shows a cross-sectional drawing of Embodiment 6 of a defogging material according to the present invention. On a light-transmitting plate material 22, the same film structure as shown in Figure 11 is formed. In other words, a transparent metal thin film 24 is formed, and on its surface, a mixed layer 34 containing a photocatalytic substance and a hydrophilic substance is formed. On the back of the light-transmitting plate material 22, similarly to the structure shown in Embodiment 4 (Figure 12), a TiO2 film 36, a SiO2 film 38 and a reflection film 40 are formed in laminated layers. Alternatively, in this embodiment as well, the surface of the mixed layer of a photocatalytic substance and a hydrophilic substance can be formed porously.

    [0055] Alternatively, in Embodiments 4 to 6 for carrying out the present invention, eliminating a reflection film 40 and constructed as a light-transmitting colored defogging substrate, the material can be used for lenses, window glass, or the like.

    Embodiment 7



    [0056] Figure 18 shows a cross-sectional drawing of Embodiment 7 of a defogging material according to the present invention. On a light-transmitting plate material 22, the same film structure as shown in Figure 1 is formed. In other words, a transparent metal thin film 24 comprising Cr, Rh, or the like is formed using a vacuum deposition method, sputtering method, or the like and further on the surface of the transparent metal thin film 24, a hydrophilic functional layer 26 containing a photocatalytic substance is formed. The hydrophilic functional layer 26 containing a photocatalytic substance comprises, from the side of the transparent metal thin film 24, a photocatalytic layer 28 containing a photocatalytic substance comprising TiO2 or the like and a hydrophilic layer 30 containing a hydrophilic substance comprising SiO2 or the like, which are formed in laminated layers using a vacuum deposition method, sputtering method, or the like. Alternatively, in this embodiment for carrying out the invention, to improve hydrophilicity further, the surface of a hydrophilic layer 30 containing a photocatalytic substance can be formed porously. On the back of a light-transmitting plate material 22, a transparent electrode film 42 comprising ITO, SnO2, etc, and on its back, a solid-phase electrochromic layer 44 comprising three layers of an oxidation coloring layer such as IrOx, NiOx, or the like, an electrolyte such as Ta2O6 or the like and a reduction coloring layer such as WO3, MoO3, or the like is formed using a vacuum deposition method, sputtering method, or the like. Further, on the back of the solid-phase electrochromic layer 44, an electrode and reflective film 46 comprising Cr, Al, or the like is formed using a vacuum deposition method, sputtering method, or the like. The transparent electrode film 42 and the electrode and reflective film 46 are conducted to electrodes (not shown) respectively. By applying electricity to these, an oxidation-reduction reaction takes place at the solid-phase electrochromic layer 44 and this defogging mirror changes to a glare-proof (colored) state. Alternatively, to prevent corrosion of the electrode and reflective film 46, a sealed resin or a sealed substrate (not shown) can be provided on a surface contacting the exterior of the electrode and reflective film 46.

    [0057] Next, spectral reflectance of a mirror shown in Figure 18 and conventional mirrors are described. Here, it is presumed that a mirror shown in Figure 18 is formed and comprises photocatalytic layer 28 containing a photocatalytic substance comprising TiO2 with a film thickness of 50nm, and a hydrophilic layer 30 containing a hydrophilic substance comprising SiO2 with a film thickness of 10nm. Figure 19 shows a structure of a section of a conventional solid-phase electrochromic glare-proof mirror. On the back of the light-transmitting plate material 22, similarly to the structure shown in Figure 18, a transparent electrode film 42, and furthermore on its back, a solid-phase electrochromic layer 44 comprising three layers of an oxidation coloring layer, an electrolyte and a reduction coloring layer and an electrode-reflection dual function film 46 are provided. Additionally, an electrode structure and a glare-proof (coloring) action are the same as those in the structure shown in Figure 18.

    [0058] Figure 20 shows a structure of a solid-phase electrochromic glare-proof defogging mirror with a TiO2 film 4 and a SiO2 film 6 of a conventional defogging mirror shown in Figure 2 being laminated on a conventional solid-phase electrochromic glare-proof mirror shown in Figure 19. On the surface of a light-transmitting plate material 22, a photocatalytic substance film 4 is provided, and furthermore on its surface, a SiO2 film 6 is provided. On the back of the light-transmitting plate material 22, similarly to the structure shown in Figure 18, a transparent electrode film 42 is provided, and furthermore on its back, a solid-phase electrochromic layer 44 comprising three layers of an oxidation coloring layer, an electrolyte and a reduction coloring layer and an electrode is provided, and furthermore on its back an electrode-reflection dual function film 46 are provided. Additionally, an electrode structure and a glare-proof (coloring) action are the same as those in the structure shown in Figure 18. Here, the mirror shown in Figure 18 is considered to be formed with a TiO2 film at a thickness of 200nm and a SiO2 film at a thickness of 10nm.

    [0059] Figure 21 shows spectral reflectance characteristics in a visible region (380~780nm) when structures shown in Figures 18, 19 and 20 respectively change to a colored state. Spectral reflectance characteristics of the structure shown in Figure 18 in the embodiment according to the present invention and of the conventional electrochromic mirror without a hydrophilic film with the structure shown in Figure 19 do not show peaks with distinguishable reflectance in a visible region. Meanwhile, in the case of the structure shown in Figure 20 with a conventional hydrophilic film, a peak with high reflectance appears within the limits of wavelength from 430nm to 470nm. This is because a thicker TiO2 film is provided to improve a photocatalytic property and an optical interference action takes place. Thus, with the structure having a conventional hydrophilic film shown in Figure 20, because a peak with high reflectance appears within the wavelength limits of a visible region, a glare-proof effect being displayed by an electrochromic layer is obstructed. In the case of a mirror with such reflectance characteristics as that of the structure shown in Figure 19, because a color tone by a peak wavelength appears on a reflection image and obstructs coloring caused by an electrochromic element, it is not suitable to be used for an electrochromic defogging mirror. However, the structure shown in Figure 18 according to the present invention does not have a peak with high reflectance in the reflectance characteristics and it is suitable to be used for an electrochromic glare-proof mirror with a defogging function.

    [0060] Alternatively, the structure shown in Figure 18, in place of an electrode-reflection dual function film 46, by forming a transparent electrode film such as ITO or the like, can be used for a solid-phase electrochromic glare-proof defogging light-transmitting substrate.

    Embodiment 8



    [0061] Figure 22 shows a cross-sectional drawing of Embodiment 8 of a defogging material according to the present invention. On a light-transmitting plate material 22, the same film structure as shown in Figure 10 is formed. In other words, a transparent metal thin film 24 and further, a hydrophilic layer 32 comprising a photocatalytic substance are formed. Alternatively, in this embodiment for carrying out the invention, to improve hydrophilicity further, the surface of a hydrophilic layer 32 containing a photocatalytic substance can be formed porously. On the back of the light-transmitting plate material 22, a transparent electrode film 42 is provided, and further, on its back, a solid-phase electrochromic layer 44 comprising three layers of an oxidation coloring layer, an electrolyte and a reduction coloring layer are provided, and furthermore on its back, an electrode-reflection dual function film 46 are provided. Additionally, an electrode structure and a glare-proof (coloring) action are the same as those of Embodiment 7 for carrying out the present invention shown in Figure 18.

    Embodiment 9



    [0062] Figure 23 shows a cross-sectional drawing of Embodiment 9 for carrying out a defogging material according to the present invention. On a light-transmitting plate material 22, the same film structure as shown in Figure 11 is formed. In other words, a transparent metal thin film 24 comprising Cr, Rh, or the like is formed, and on the surface of the transparent metal thin film 24, a mixed layer 34 containing a photocatalytic substance comprising TiO2 or the like and a hydrophilic substance comprising SiO2 or the like is formed. Alternatively, in this embodiment for carrying out the invention as well, the mixed layer 34 containing a photocatalytic substance and a hydrophilic substance can be formed porously. On the back of the light-transmitting plate material 22, a transparent electrode film 42 is provided, and further, on the back, a solid-phase electrochromic layer 44 comprising three layers of an oxidation coloring layer, an electrolyte and a reduction coloring layer are provided, and further, on the back, an electrode-reflection dual function film 46 is provided. An electrode structure and a glare-proof (coloring) action are the same as those of Embodiment 7 for carrying out the present invention shown in Figure 18.

    Embodiment 10



    [0063] Figure 24 shows a cross-sectional drawing of Embodiment 10 of a defogging material according to the present invention. A light-transmitting plate material 22 comprises a structure wherein a liquid-phase electrochromic layer 52 composed of (a) an electrolyte solution comprising (i) an electrochromic substance selected from WO3, MoO3, IrOx, NiOx, or the like, (ii) an electrolyte such as Lil, LiClO4, or the like, and (iii) solvent such as r-butyrolactone, propylenecarbonate or the like and/or an ultraviolet absorbent such as benzophenone and cyanoacrylate or the like, or (b) an electrochromic solution comprising (I) an electrochromic substance such as viologen or the like and (II) a solvent such as r-butyrolactone, propylenecarbonate, or the like and/or an ultraviolet absorbent such as benzophenone and cyanoacrylate, or the like is interposed between the first light-transmitting substrate 48 and the second light-transmitting substrate 50. Further, on the surfaces opposite to the first light-transmitting substrate 48 and the second light-transmitting substrate 50, the first and second transparent electrode films 54 and 56 comprising ITO, SnO2, or the like are provided, respectively. Additionally, the surroundings of the liquid-phase electrochromic layer 52 are sealed by a sealing material 60 composed of an adhesive or the like to prevent the solution from leaking. On the surface of the light-transmitting plate material 22, the same film structure as that shown in Figure 1 is formed. In other words, a transparent metal thin film 24 is formed, and furthermore on its surface, a hydrophilic functional layer 26 containing a photocatalytic substance is provided. The hydrophilic functional layer 26 containing a photocatalytic substance comprises, from the side of the hydrophilic functional layer 26, a photocatalytic layer 28 containing a photocatalytic substance comprising TiO2 or the like and a hydrophilic layer 30 containing a hydrophilic substance comprising SiO2 or the like, which are formed in laminated layers. Alternatively, in this embodiment for carrying out the invention, to improve hydrophilicity further, the surface of a hydrophilic layer 30 containing a hydrophilic substance can be formed porously. On the back of the light-transmitting plate material 22, a reflection film 24 comprising Cr, Al, or the like is formed using a vacuum deposition method, sputtering method, or the like The first transparent electrode film 54 and the second transparent electrode film 56 are electrically connected to electrodes (not shown), respectively. By applying electricity to these, an oxidation-reduction reaction takes place at the liquid-phase electrochromic layer 44 and this defogging mirror of Embodiment 10 for carrying out the present invention changes to a glare-proof (colored) state.

    [0064] Alternatively, in place of a hydrophilic functional layer 26 containing a photocatalytic substance, similarly to Embodiment 8 for carrying out the present invention (Figure 22), the same effect can be obtained by constructing a hydrophilic layer 32 comprising a hydrophilic substance.

    [0065] Alternatively, in place of a hydrophilic functional layer 26 containing a photocatalytic substance, similarly to Embodiment 9 for carrying out the present invention (Figure 23), the same effect can be obtained by constructing a hydrophilic layer 32 comprising a photocatalytic substance.

    [0066] Additionally, not providing a reflection film 40 and constructing as a light-transmitting liquid-phase electrochromic defogging material, this material can be used as a light controlling window or the like.

    [0067] Alternatively, without using a reflection film 40, by replacing the second transparent electrode film 56 with an electrode-reflection dual function film, a liquid-phase electrochromic glare-proof defogging mirror can be obtained.

    [0068] Alternatively, to prevent corrosion of the first and the second transparent electrode films 54 and 56 by a solvent used for the liquid-phase electrochromic layer 52, an electrode protective layer comprising light-transmitting SiO2 or the like can be provided between the first and the second transparent electrode films 54 and 56 and the liquid-phase electrochromic layer 52.

    Industrial Applicability



    [0069] As described above, a composite material according to the present invention can be used, by applying to a mirror, for automobile outer mirrors as a defogging mirror, as a colored defogging mirror wherein a reflection surface is colored, or as an electrochromic glare-proof mirror. Further, the composite material can be used for a lens, a window, and the like, by constructing a light-transmitting colored defogging plate without providing a reflection film, or the composite material can be used for a light-adjusted window by constructing a light-transmitting liquid-phase electrochromic defogging material.


    Claims

    1. A composite material comprising

    - a base material,

    - a transparent metal thin film formed on a surface of the base material having a thickness of between 1.0 and 10.0 nm and

    - a hydrophilic functional layer containing a photocatalytic substance formed on a surface of the transparent metal thin film,

    wherein the transparent metal thin film reflects ultraviolet rays to re-enter the photocatalyst containing layer.
     
    2. The composite material according to Claim 1, wherein said base material comprises a light-transmitting material.
     
    3. The composite material according to Claim 1, wherein said base material comprises a plate material.
     
    4. The composite material according to Claim 3, wherein said base material comprises a light-transmitting plate material.
     
    5. The composite material according to Claim 4, wherein a reflection film is formed on the back of said light-transmitting plate material to configure said light-transmitting plate material as a defogging mirror.
     
    6. The composite material according to Claim 4, wherein said light-transmitting plate material comprises a light-transmitting colored plate material which has light wavelength selectivity.
     
    7. The composite material according to Claim 6, wherein a reflection film is formed on the back of said light-transmitting plate material to configure said light-transmitting plate material as a defogging mirror.
     
    8. The composite material according to Claim 4, wherein said light-transmitting plate material comprises two light-transmitting substrates, a liquid-phase electrochromic layer interposed therebetween, and transparent electrode films provided on the respective opposite surfaces of said two light-transmitting substrates.
     
    9. The composite material according to Claim 8, wherein a reflection film is formed on the back of said light-transmitting plate material to configure said light-transmitting plate material as a defogging mirror.
     
    10. The composite material according to Claim 4, wherein a first transparent electrode film, a solid-phase electrochromic layer, and a second transparent electrode film are formed in sequence in laminated layers on the back of the light-transmitting substrate to configure said light-transmitting plate material as a defogging mirror.
     
    11. The composite material according to Claim 3, wherein a transparent electrode film, a solid-phase electrochromic layer, and an electrode-reflection dual function film are formed in sequence in laminated layers on the back of the light-transmitting substrate to configure said plate material as a defogging mirror.
     
    12. The composite material according to Claim 3, wherein said plate material comprises (i) a light-transmitting substrate with a transparent electrode film formed on one side of the light-transmitting substrate, (ii) a substrate with an electrode-reflection dual function film formed on one side of the substrate, (iii) a liquid-phase electrochromic layer interposed between said light-transmitting substrate and said substrate, wherein said transparent electrode film and said electrode-reflection dual function film face each other, to configure said plate material as a defogging mirror.
     
    13. The composite material according to Claim 5, 7, 9, 11 or 12, which is configured as an outer mirror for automobile use.
     
    14. The composite material according to Claim 1, wherein said hydrophilic functional layer containing said photocatalytic substance comprises as a main element a laminate of, from the side of said base material, a photocatalyst layer containing a photocatalytic substance and a hydrophilic layer containing a hydrophilic substance.
     
    15. The composite material according to Claim 4, wherein said hydrophilic layer containing said hydrophilic substance has a layer thickness of 50nm or less
     
    16. The composite material according to Claim 1, wherein said hydrophilic functional layer containing said photocatalytic substance comprises as its main element a mixed layer containing a photocatalytic substance and a hydrophilic substance.
     
    17. The composite material according to Claim 13, wherein the main component of said photocatalytic substance is TiO2 and the main component of said hydrophilic substance is SiO2.
     
    18. The composite material according to Claim 1, wherein said hydrophilic functional layer containing said photocatalytic substance comprises as a main element a layer which comprises a photocatalytic substance.
     
    19. The composite material according to Claim 18, wherein the main component of said photocatalytic substance is TiO2.
     
    20. The composite material according to Claim 1, wherein the surface of the hydrophilic functional layer containing said photocatalytic substance is porous.
     
    21. The composite material according to Claim 1, wherein said transparent metal thin film comprises as a main component Cr, Rh, Ag, Pt, Al or a mixture of the foregoing.
     


    Ansprüche

    1. Verbundmaterial, umfassend

    - ein Basismaterial,

    - eine transparente Metall-Dünnschicht, die auf einer Oberfläche des Basismaterials gebildet ist, die eine Dicke von zwischen 1,0 und 10,0 nm aufweist, und

    - eine hydrophile funktionelle Lage, enthaltend eine photokatalytische Substanz, gebildet auf einer Oberfläche der transparenten Metall-Dünnschicht,

    wobei die transparente Metall-Dünnschicht ultraviolette Strahlen so reflektiert, daß diese in die Photokatalysator-enthaltende Schicht wieder eintreten.
     
    2. Verbundmaterial nach Anspruch 1, wobei das Basismaterial ein lichtdurchlässiges Material umfaßt.
     
    3. Verbundmaterial nach Anspruch 1, wobei das Basismaterial ein Beschichtungsmaterial umfaßt.
     
    4. Verbundmaterial nach Anspruch 3, wobei das Basismaterial ein lichtdurchlässiges Beschichtungsmaterial umfaßt.
     
    5. Verbundmaterial nach Anspruch 4, wobei auf der Rückseite des lichtdurchlässigen Beschichtungsmaterials ein Reflektionsfilm gebildet ist, um das lichtdurchlässige Beschichtungsmaterial als einen nicht beschlagenden Spiegel zu konfigurieren.
     
    6. Verbundmaterial nach Anspruch 4, wobei das lichtdurchlässige Beschichtungsmaterial ein lichtdurchlässiges gefärbtes Beschichtungsmaterial umfaßt, das eine Licht-Wellenlängen-Selektivität aufweist.
     
    7. Verbundmaterial nach Anspruch 6, wobei ein Reflektionsfilm auf der Rückseite des lichtdurchlässigen Beschichtungsmaterials gebildet ist, um das lichtdurchlässige Beschichtungsmaterial als einen nicht beschlagenden Spiegel zu konfigurieren.
     
    8. Verbundmaterial nach Anspruch 4, wobei das lichtdurchlässige Beschichtungsmaterial zwei lichtdurchlässige Substrate, eine Flüssigphase-elektrochrome Schicht, die dazwischen gelagert ist, und transparente Elektrodenschichten, die auf den jeweilig gegenüberliegenden Oberflächen von zwei lichtdurchlässigen Substraten zur Verfügung gestellt werden, umfaßt.
     
    9. Verbundmaterial nach Anspruch 8, wobei auf der Rückseite des lichtdurchlässigen Beschichtungsmaterials ein Reflektionsfilm gebildet ist, um das lichtdurchlässige Beschichtungsmaterial als einen nicht beschlagenden Spiegel zu konfigurieren.
     
    10. Verbundmaterial nach Anspruch 4, wobei ein erster durchsichtiger Elektrodenfilm, eine Festphase-elektrochrome Lage und ein zweiter durchsichtiger Elektrodenfilm in Sequenz in laminierten Schichten auf der Rückseite des lichtdurchlässigen Substrats gebildet sind, um das lichtdurchlässige Beschichtungsmaterial als einen nicht beschlagenden Spiegel zu konfigurieren.
     
    11. Verbundmaterial nach Anspruch 3, wobei eine durchsichtige Elektrodenschicht, eine Festphase-elektrochrome Lage und ein Elektroden-Reflektions-Dualfunktionsfilm in Sequenz in laminierten Lagen auf der Rückseite des lichtdurchlässigen Substrats gebildet sind, um das Beschichtungsmaterial als einen nicht beschlagenden Spiegel zu konfigurieren.
     
    12. Verbundmaterial nach Anspruch 3, wobei das Beschichtungsmaterial umfaßt; (i) ein lichtdurchlässiges Substrat mit einem transparenten Elektrodenfilm, gebildet auf einer Seite des lichtdurchlässigen Substrats, (ii) ein Substrat mit einem Elektroden-Reflektions-Dualfunktionsfilm, gebildet auf einer Seite des Substrats; (iii) eine Flüssigphase-elektrochrome Lage, die zwischen das lichtdurchlässige Substrat und das Substrat worin der durchsichtige Elektrodenfilm und der Elektroden-Reflektions-Dualfunktionsfilm einander gegenüberliegen dazwischen gelagert ist, um das Beschichtungsmaterial als einen nicht beschlagenden Spiegel zu konfigurieren.
     
    13. Verbundmaterial nach Anspruch 5, 7, 9, 11 oder 12, das als ein Außenspiegel zur Verwendung in Automobilen konfiguriert ist.
     
    14. Verbundmaterial nach Anspruch 1, wobei die hydrophile funktionelle Lage, die die photokatalytische Substanz enthält, als ein Hauptelement von der Seite des Basismaterials ein Laminat aus einer Photokatalysatorlage, enthaltend eine photokatalytische Substanz und einer hydrophilen Lage, enthaltend eine hydrophile Substanz, umfaßt.
     
    15. Verbundmaterial nach Anspruch 4, wobei die hydrophile Lage, die die hydrophile Substanz enthält, eine Lagendicke von 50 nm oder weniger aufweist.
     
    16. Verbundmaterial nach Anspruch 1, wobei die hydrophile funktionelle Lage, die die photokatalytische Substanz enthält, als ihr hauptsächliches Element eine gemischte Lage umfaßt, die eine photokatalytische Substanz und eine hydrophile Substanz umfaßt.
     
    17. Verbundmaterial nach Anspruch 13, wobei die Hauptkomponente der photokatalytischen Substanz TiO2 und die Hauptkomponente der hydrophilen Substanz SiO2 ist.
     
    18. Verbundmaterial nach Anspruch 1, wobei die hydrophile funktionelle Lage, die die photokatalytische Substanz enthält, als ein Hauptelement eine Lage umfaßt, die eine photokatalytische Substanz umfaßt.
     
    19. Verbundmaterial nach Anspruch 18, wobei die Hauptkomponente der photokatalytischen Substanz TiO2 ist.
     
    20. Verbundmaterial nach Anspruch 1, wobei die Oberfläche der hydrophilen funktionellen Lage, die die photokatalytische Substanz enthält, porös ist.
     
    21. Verbundmaterial nach Anspruch 1, wobei die durchsichtige Metall-Dünnschicht als eine Hauptkomponente Cr, Rh, Ag, Pt, Al oder im Gemisch der voranstehenden umfaßt.
     


    Revendications

    1. Matériau composite comprenant :

    - un matériau de base,

    - un film mince métallique transparent formé sur une surface du matériau de base ayant une épaisseur comprise entre 1,0 et 10,0 nm et

    - une couche fonctionnelle hydrophile contenant une substance photocatalytique formée sur une surface du film mince métallique transparent,

    dans lequel le film mince métallique transparent reflète les rayons ultraviolets pour qu'ils pénètrent de nouveau la couche contenant un photocatalyseur.
     
    2. Matériau composite selon la revendication 1, dans lequel ledit matériau de base comprend un matériau transmettant la lumière.
     
    3. Matériau composite selon la revendication 1, dans lequel ledit matériau de base comprend un matériau en plaque.
     
    4. Matériau composite selon la revendication 3, dans lequel ledit matériau de base comprend un matériau en plaque transmettant la lumière.
     
    5. Matériau composite selon la revendication 4, dans lequel un film réfléchissant est formé sur l'envers dudit matériau en plaque transmettant la lumière pour que ledit matériau en plaque transmettant la lumière soit configuré comme un miroir désembueur.
     
    6. Matériau composite selon la revendication 4, dans lequel ledit matériau en plaque transmettant la lumière comprend un matériau en plaque transmettant la lumière coloré qui a une sélectivité de longueurs d'onde de lumière.
     
    7. Matériau composite selon la revendication 6, dans lequel un film réfléchissant est formé sur l'envers dudit matériau en plaque transmettant la lumière pour que ledit matériau en plaque transmettant la lumière soit configuré comme un miroir désembueur.
     
    8. Matériau composite selon la revendication 4, dans lequel ledit matériau en plaque transmettant la lumière comprend deux substrats transmettant la lumière, une couche électrochromique en phase liquide interposée entre eux, et des films d'électrode transparents disposés sur les surfaces opposées respectives desdits deux substrats transmettant la lumière.
     
    9. Matériau composite selon la revendication 8, dans lequel un film réfléchissant est formé sur l'envers dudit matériau en plaque transmettant la lumière pour que ledit matériau en plaque transmettant la lumière soit configuré comme un miroir désembueur.
     
    10. Matériau composite selon la revendication 4, dans lequel un premier film d'électrode transparent, une couche électrochromique en phase solide, et un second film d'électrode transparent sont formés en séquence en couches stratifiées sur l'envers du substrat transmettant la lumière pour que ledit matériau en plaque transmettant la lumière soit configuré comme un miroir désembueur.
     
    11. Matériau composite selon la revendication 3, dans lequel un film d'électrode transparent, une couche électrochromique en phase solide, et un film ayant une double fonction d'électrode et de réflexion sont formés en séquence en couches stratifiées sur l'envers du substrat transmettant la lumière pour que ledit matériau en plaque soit configuré comme un miroir désembueur.
     
    12. Matériau composite selon la revendication 3, dans lequel ledit matériau en plaque comprend (i) un substrat transmettant la lumière avec un film d'électrode transparent formé sur un côté du substrat transmettant la lumière, (ii) un substrat avec un film ayant une double fonction d'électrode et de réflexion formé sur un côté du substrat, (iii) une couche électrochromique en phase liquide interposée entre ledit substrat transmettant la lumière et ledit substrat, dans lequel ledit film d'électrode transparent et ledit film ayant une double fonction d'électrode et de réflexion se font mutuellement face, pour que ledit matériau en plaque soit configuré comme un miroir désembueur.
     
    13. Matériau composite selon la revendication 5, 7, 9, 11 ou 12, qui est configuré comme un rétroviseur extérieur d'automobile.
     
    14. Matériau composite selon la revendication 1, dans lequel ladite couche fonctionnelle hydrophile contenant ladite substance photocatalytique comprend, à titre d'élément principal, un stratifié, en partant du côté dudit matériau de base, une couche de photocatalyseur contenant une substance photocatalytique et une couche hydrophile contenant une substance hydrophile.
     
    15. Matériau composite selon la revendication 4, dans lequel ladite couche hydrophile contenant ladite substance hydrophile a une épaisseur de couche de 50 nm ou moins.
     
    16. Matériau composite selon la revendication 1, dans lequel ladite couche fonctionnelle hydrophile contenant ladite substance photocatalytique comprend, à titre d'élément principal, une couche mixte contenant une substance photocatalytique et une substance hydrophile.
     
    17. Matériau composite selon la revendication 13, dans lequel le composant principal de ladite substance photocatalytique est TiO2 et le composant principal de ladite substance hydrophile est SiO2.
     
    18. Matériau composite selon la revendication 1, dans lequel ladite couche fonctionnelle hydrophile contenant ladite substance photocatalytique comprend, à titre d'élément principal, une couche qui comprend une substance photocatalytique.
     
    19. Matériau composite selon la revendication 18, dans lequel le composant principal de ladite substance photocatalytique est TiO2.
     
    20. Matériau composite selon la revendication 1, dans lequel la surface de la couche fonctionnelle hydrophile contenant ladite substance photocatalytique est poreuse.
     
    21. Matériau composite selon la revendication 1, dans lequel ledit film mince métallique transparent comprend, à titre de composant principal, Cr, Rh, Ag, Pt, Al ou un mélange des précédents.
     




    Drawing









































    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description